Process for producing flowable compounds of acetyl cellulose.



30 found, however, that when that process is WILLIAM G. LINDSAY, OFCALDWELL, NEW JERSEY, ASSIGNOR TO THE CELLUIAOD COMPANY, OF NEW YORK, N.Y., A CORPORATION OF. NEW JERSEY.

PROCESS FOR IPRODUCING FLO'WAIBLE COMPOUNDS OF ACETYL CELL'ULOSE.

Specification of Letters Patent.

No Drawing. Application filed November 6, 1911, Serial No. 658,785.Renewed March 19, 1917. Serial To all whom itmag concern: 7

Be it known that I, WILLIAM G. LINDSAY,

a citizen of the United States, residing in.

substances, sometimes in their original finished form with or withoutincorporated colors, and sometimes as films which are used forphotographic and other purposes.

Although the final or useful formof the different compounds of acetylcellulose is that of, a solid or dried material, the different processesof conversion into this final solid form involve, as is well understood,the employment of solutions or mixtures of varying consistency as toplasticity, stiifness or fluidity, depending generally upon theproportion and kind of solvent used to the amount of the originalbase-acetyl cellulose.

It has long been known that camphor mixed with nitro cellulose upon theaddition of ethyl alcohol to the mixture becomes a solvent of-the nitrocellulose. I have appliedto acetyl cellulose no solvent action takesplace in the cold, and the object of my invention was to find substanceswhich, when added to the acetyl cellulose would, upon the subsequentaddition of ethyl alcohol, exert a solvent action upon the acetyl.cellulose and produce a plastic mass which could be worked in amanneranalogous to. nitro cellulose-camphorcompounds.

I have discovered that not all of the so called camphor substitutespossess this property when used with acetyl cellulose, and in solventswhen melted, but are non-solvents when dissolved in ethyl alcohol atroom temperature, such as camphor, tetrachlorethyl acetanilid, andtrichlormethyl acetanilid.

Class C: Such substances as become solvents when melted and also becomesolvents Patented Oct. 23, 1917,

when dissolved in methyl or ethyl alcohol in equal parts by weight atroom temperature; such as toluol-sulfonamid, ethyl paratoluolsulfonamid, benzene-sulfonamid, ethyl acetanilid, and methylacetanilid.

I have also discovered that in making flowable solutions from my newcompounds, I can employ substances other than those mentioned, and Ihave accordingly divided this application' into -four divisions, eachforming the subject of a separate application and designated by theletters A (Ser. No. 658,783); B (Ser. No. 658,784); 0 (Ser. No.658,785); and D (Ser. No. 658,786); respectively, all filed on November6, 1911.

In order to carry out the new process which forms the subject matter ofthis application (Division C), as one example, I incorporate 100 partsof an acetyl cellulose which is soluble in acetone with 20 to 50 partsof ethyl para toluol-sulfonamid by suitable grinding and mixing, as isthe practice in the nitro cellulose art. To such mixture I add from 40to 100 parts of ethyl or of methyl alcohol, or a mixture of the two, andafter thorough incorporation by stirring, the mixture is allowed toremain at room temperature in a closed vessel for from 5 to 24 hours, orlonger, the length of time depending upon the physical form of theacetyl cellulose used; that is, whether it is finely or. coarselyground. In the course of time the mixture will have become convertedinto a more or less stifl' gelatinated mass. It can then be worked up onrolls or a kneading machine, according to the practice which is commonin the nitro cellulose-camphor plastic art, and the resulting productmay then be inolded or passed through the stufiing machine as in thecase of nitro cellulose-camphor compounds' I have found that a mixturecomposed of 1 part by weight each of ethyl alcohol and ethyl paratoluol-sulfonamid is a more hence it is desirable to use as small aproportion of alcohol as. possible in converting the acetyl celluloseinto a gelatinous mass, but the application of heat will restore to acertain extent the solvent action of a solvent mixture which isotherwise too weak. A proportion of 1.5 parts of ethyl or methyl alcoholto 1 part of ethyl para toluol-sulfonamid also produces verysatisfactory results as a gelatinating agent for acetyl cellulose.

Instead of the ethyl para 'toluolsulfonamid I can usebenzene-sulfonamid, and also ethyl acetanilid and related derivatives.

In order to produce flowable solutions in the cold from the gelatinousmass made according to the process above described and solutions whichare suitable for filtering, etc., I have found that suitable solvents ordiluents for such purposes are produced by incorporating with the mass,mixtures of either ethyl or methyl alcohol with the following liquids inthe proportions hereinafter described. These liquids are choloroform,epichlorhydrin, acetodichlorhydrin, dichlorethylene, ethylene-chlorid,trichlorhydrin, pentachlorethane, aeetochlorhydrin,acetylene-tetrachlorid, chloracetate of ethyl, acetone, ethylacetate,and di-acetochlorhy drin.

A proportion of the chloroform ingredient equal to 10 to 40% of thealcohol ingredient in the process is a suitable proportion.

A mixture produced by combining'one of the above liquids with an equalvolume of methyl or of ethyl .alcohol, or a mixture of the two, willproduce a solvent for acetyl cellulose of the acetone soluble variety.

- I have discovered, also, that when the proportion of methyl or ethylalcohol is increased beyond the proportion to produce a solvent mixture,the addition of a camphor substitute of Class C reestablishes thesolvent action.

In order to convert the gelatinous mass produced according to theprocess above described into a more fluid mixture which can be filtered,etc., I use a mixture of methyl or ethyl alcohol containing from 20% to40% by volume of any of the above liquid substances such as chloroform,epichlorhydrin, etc. To 1 part of the gelatinous mass I add from 1 to 4parts of this compound solvent, or suflicient to produce a product ofthe desired fluidity, and incorporate it by mixing, kneading, stirringor malaxating. After filtration or other treatment, the solution ofacetyl cellulose thus produced is worked up in the usual manner byevaporating the excess of solvent and further kneading, pressing, etc.,the resultant mass. Here, again, I have found that if the solvent is tooweak, the application of heat will restore the solvent action.

If it is desired to produce a non-inflamacetochlorhydrin,

mability of the plastic masses made by the 'use of camphor substitutesof Class C can be reduced and overcome by incorporating such camphorsubstitutes as triphenylphosphate which belong to Class A. I have foundthat this can be accomplished by proceeding as follows:

T incorporate with 100 parts of acetyl cellulose, 20 parts of ethyl paratoluol-sulfonamid and 20 parts of trip-henylphosphate, and afterthorough grinding, mixing, etc., I add 40 to 60 parts of methyl or ethylalcohol, but I prefer methyl alcohol. The gelatinous mass produced byallowing this mixture to stand at room temperature in an air tightreceptacle is further Worked up by kneading, etc., according topractices well known to the nitro cellulose art. If it is desired toproduce a more fluid solution, the addition of 1' to 4: parts of amixture consisting of 70 parts by volume of ethyl or methyl alcohol and30 parts by volume of dichlorethylene, ethyleneehlorid or chloroform, isadded. It will. thus be seen that the question of proportions entersvery. largely into the successfulpractice of the processes and thecompositions of the new solvents described in this specification.

The generic expression an aryl-sulfonamid in the claims comprises suchequivalent substances for the purposes of this invention astoluol-sulfonamid, ethyl para toluol-sulfonamid, and benzene-sulfonamid.Similarly, equivalents for chloroform for producing a flowable solutionin. the cold as aforesaid comprise epichlorhydrin, ace todiohlorhydrin,dichlorethylene, ethylenechlorid, trichlorhydrin, pentachlorethane,acetylene tetrachlorid, chloracetate of ethyl, acetone, ethyl acetateand di-acetochlorhydrin.

The generic expression triaryl phosphoric acid ester in the claimscomprises the same being an alkylated aromatic sulfonamid.

In order to distinguish the difierent branches of the invention orinventions described in this specification, l have, as

stated, divided the subject matter into four tion (Division C) I claimas follows:

1. The process which comprises incorporating about 100 parts of anacetone-soluble acetyl cellulose with about 20 to 50 parts of an arylsulfonamid in the presence of a small proportion of a monohydric alcoholhaving not more than two carbon atoms, and in the further presence of aliquid adapted to produce a flowable solution in the cold, theproportion of the last named ingredient being from 10 to 40% of thealcohol ingredient.

2. The process which comprises incorporating about 100 parts of anacetone-soluble acetyl-cellulose with about 20 to 50 parts of an arylsulfonamid in the presence of .a small proportion of a monohydricalcohol having not more than two carbon atoms,

and in the further presence of a liquid adapted to produce a flowablesolution in the cold.

2). The process which comprises incorporating about 100 parts of anacetone-soluble acetyl cellulose with about 20 to 50 parts of an arylsulfonamid in the presence'of a smalleproportion of a monohydric'alcohol having not more than two carbon atoms, and in the furtherpresence of chloroform.

4. The process which comprises incorporating about 100 parts of anacetone-soluble acetyl cellulose with about 20 to 50 parts of an arylsulfonamid and about 4:0 to'100 parts of a monohydric alcohol having notmore than two carbon atoms, and further incorporating a liquid adaptedto produce a flowable solution in the cold, the proportion of the lastnamed ingredient being from 10 to 40% of the alcohol ingredient.

5. The process which comprises incor 0- rating about 100 parts of anacetone-solu le acetyl cellulose with about 20 to 50 parts of an arylsulfonamid and about 4:0 to 100 parts of a .monohydric alcohol havingnot more than two carbon atoms, and further incorporating a liquidadapted to produce a flowable solution in' the cold.

6. The process which comprises incorporating about 100 parts of anacetone-soluble acetyl cellulose with a sufiicient proportion of asubstance adapted to convert the acetyl cellulose into a gelatinous massin the presence of about 40'to 100 parts of a monohydric alcohol havingnot more than two carbon atoms, and further incorporating therewith asufiicient proportion of a liquid adapted to produce a flowable solutionin the cold.

7. The process which comprises incorporating about 100 parts of anacetone-soluble acetyl cellulose withla suflicient porportion of asubstance adapted to convert the acetyl cellulose into a gelatinous massin the presence of about 40 to 100 parts of a monohydric alcohol havingnot more than two carbon atoms, and further incorporating therewith asuflicient proportion of chlorofoirin to produce a flowable solution inthe co 8. The process which comprises incorporating about 100 parts ofan acetone-soluble acetyl cellulose with about 20 parts oftriphenylphosphate and. also with about 20 parts of a substance adaptedto convert the acetyl cellulose into a gelatinous mass in the presenceof a small proportion of a monohydric alcohol having not more than twocarbon atoms, and further incorporating therewith a suflicientproportion of a liquid adapted to produce a flowable'solution in thecold.

' 9. The process which comprises incorporating about 100 parts of anacetone-soluble acetyl cellulose with about 20 parts of triarylphosphoric acid ester and also with about 20 parts of a substanceadapted to convert the acetyl cellulose into a gelatinous mass in thepresence of a small proportion of a monohydric alcohol having not morethan two carbon atoms, and further incorporating therewith a sufficientproportion of a liquid adapted to produce a flowable solution in thecold.

10. The process which comprises incorporating about 100 parts of anacetonesoluble acetyl cellulose with about 20 to 50 parts of an-arylsulfonamid, about 40 to 100 parts of a monohydric alcohol having notmore than two carbon atoms", and furv WHJLIAM G. LINDSAY.

Witnesses:

Invmo M. Wmss, J. E. HINDON HYDE.

